The Preyssler, Wells-Dowson and Keggin heteropolyacids are efficient and eco-friendly solid acid catalysts for the acylation of electron-rich aromatic compounds with acid anhydrides. The performance of different forms of heteropolyacids was compared. In all the cases, the best results were obtained using the Preyssler heteropolyacid as the catalyst. In the presence of 25 mol% (with respect to H+ equivalency) Preyssler catalyst, highly para-selective acetylation of anisole occurs using two equivalents of acetic anhydride, in 15 min at room temperature. The isolated yield of the p-methoxyacetophenone product is 98%.

A catalytic synthesis of calix[4]pyrroles and N-confused calix[4]pyrroles by reaction of dialkyl or cycloalkyl ketones with pyrrole was performed using Preyssler, sodium30-tungsto pentaphosphate, [NaP5W30O 110]14- and Wells-Dawson heteropolyacids as acidic catalysts. The process occurred under mild, eco-friendly and environmental friendly conditions and as a reusable, green catalyst at room temperature for 6 hours. The results showed that the yield for this synthesis is excellent with the use of Preyssler and Wells-Dawson type tungstophosphoric heteropolyacid, H6[P2W18O62], catalysts. The synthesis reaction of calix[4]pyrroles and N-confused calix[4]pyrroles was developed using different solvents and the best yields were obtained in chloroform.